4-Quinolinol derivatives and agrohorticultural bactericides containing the same as active ingredient

ABSTRACT

A new agricultural and horticultural fungicide having an excellent control effect is provided. 4-Quinolinol derivatives represented by the following formula:                    
     or agriculturally and horticulturally acceptable acid addition salts thereof.

This application is the 371 of PCT/JP98/02434, filed on Jun. 2, 1998.

FIELD OF THE INVENTION

The present invention relates to 4-quinolinol derivatives andagricultural and horticultural fungicides containing them as activeingredients.

BACKGROUND OF THE INVENTION

JP-01246263A, JP-05202032A, JP-05271222A and JP-07285938A, which werepublished prior to the filing date of the present application, disclosethat quinoline derivatives having a substituent, such as aryloxy,arylthio, amino, pyrimidyloxy, pyrimidylthio or benzoyl group, at4-position of quinoline skeleton are effective against plant pathogenicfungi and useful as agricultural and horticultural fungicides. However,it has never known that a quinoline derivative having an acyloxy groupat 4-position of quinoline skeleton has an excellent fungicidalactivity.

And, JP-03128355A discloses 4-acyloxyquinoline derivatives structurallysimilar to the compound of the present invention and insecticidal andacaricidal agents containing them as active ingredients. However, it hasnever known that these compounds are effective against plant pathogenicfungi.

DISCLOSURE OF THE INVENTION

Many active agents having control effect against various plant diseaseswere discovered and various agricultural and horticultural fungicidescontaining them as active ingredients have been developed. Due to someproblems, such as an appearance of resistant fungi, however, fungicideshaving higher control effect are needed.

Thus, an object of the present invention is to provide a newagricultural and horticultural fungicide having higher control effect.

The present inventors concentrated on solving the above-mentionedproblem. As the result, it was found that among 4-quinolinolderivatives, 4-quinolinol derivatives having specific substituents atall of the 2, 3 and 5 to 8 positions of quinoline skeleton and theiracid addition salts show excellent fungicidal activity against variousplant pathogenic fungi causing blast of rice, brown spot of rice,powdery mildew of Cucurbitaceae, anthracnose of potato and the like, andthereby the present invention was completed.

Accordingly, the present invention relates to a 4-quinolinol derivativerepresented by the general formula (I):

wherein

R¹ represents

a hydrogen atom,

an alkali metal,

an alkaline earth metal, or

COR⁴ in which R⁴ is

a hydrogen atom,

an optionally substituted C₁-C₁₈ alkyl group,

an optionally substituted C₂-C₁₈ alkenyl group,

an optionally substituted C₃-C₁₀ cycloalkyl group,

an optionally substituted phenyl lower alkyl group,

an optionally substituted phenoxy lower alkyl group,

an optionally substituted aryl group,

OR⁵ in which R⁵ is an optionally substituted lower alkyl group, anoptionally substituted aryl group, an optionally substitutedheterocycle, an optionally substituted phenyl lower alkyl group or anoptionally substituted phenoxy lower alkyl group, or

NR⁶R⁷ in which R⁶ and R⁷ are each a hydrogen atom, an optionallysubstituted C₁-C₆ alkyl group or an optionally substituted phenyl group,or R⁶ and R⁷ together with N may form a four- to six-membered ringcontaining one or two heteroatoms;

R² represents an optionally substituted lower alkyl group;

R³ represents

an optionally substituted C₁-C₁₈ alkyl group,

an optionally substituted lower alkenyl group, or

an optionally substituted lower alkoxy group; or

R² and R³ together represent —(CH₂)m— in which m is 3 or 4; and

W represents 1 to 4 substituents on the nucleus which may be identicalor different and each of which is

a halogen atom,

an optionally substituted C₁-C₁₀ alkyl group,

an optionally substituted lower alkenyl group,

an optionally substituted lower alkynyl group,

an optionally substituted C₁-C₁₀ alkoxy group,

an optionally substituted C₃-C₁₀ cycloalkyl group,

an optionally substituted aryl group,

an optionally substituted aryloxy group,

NR⁸R⁹ in which R⁸ and R⁹ are each a hydrogen atom, an optionallysubstituted C₁-C₆ alkyl group or an optionally substituted phenyl group,or R⁸ and R⁹ together with N may form a four- to six-membered ringcontaining one or two heteroatoms,

COR¹⁰ in which R¹⁰ is a hydrogen atom, an optionally substituted loweralkyl group or an optionally substituted lower alkenyl group,

COOR¹¹ in which R¹¹ is a hydrogen atom, an optionally substituted loweralkyl group or an optionally substituted lower alkenyl group,

a nitro group or

a cyano group,

and acid addition salts thereof as well as an agricultural andhorticultural fungicide containing at least one of them.

In the 4-quinolinol derivatives represented by the aforementionedgeneral formula (I),

R¹ represents

a hydrogen atom,

an alkali metal, such as preferably sodium and potassium,

an alkaline earth metal, such as magnesium, calcium and barium, in whichmagnesium and calcium are preferable, or

COR⁴ in which R⁴ is

a hydrogen atom,

an optionally substituted C₁-C₁₈ alkyl group, preferably an optionallysubstituted C₁-C₈ alkyl group, more preferably a C₁-C₄ alkyl group, suchas methyl, ethyl, propyl, isopropyl, butyl, isobutyl and t-butyl,

an optionally substituted C₂-C₁₈ alkenyl group, preferably an optionallysubstituted C₂-C₈ alkenyl group, more preferably a C₂-C₄ alkenyl group,such as vinyl group CH₂═CH—, allyl group CH₂═CHCH₂— and 2-butenyl groupCH₃CH═CHCH₂—,

an optionally substituted C₃-C₁₀ cycloalkyl group, preferably anoptionally substituted C₃-C₆ cycloalkyl group,

an optionally substituted phenyl lower alkyl group,

an optionally substituted phenoxy lower alkyl group,

an optionally substituted aryl group,

OR⁵ in which R⁵ is an optionally substituted lower alkyl group, anoptionally substituted aryl group, an optionally substitutedheterocycle, an optionally substituted phenyl lower alkyl group or anoptionally substituted phenoxy lower alkyl group, or

NR⁶R⁷ in which R⁶ and R⁷ are each a hydrogen atom, an optionallysubstituted C₁-C₆ alkyl group or an optionally substituted phenyl group,or R⁶ and R⁷ together with N may form a four- to six-membered ringcontaining one or two heteroatoms;

R² represents an optionally substituted C₁-C₄ alkyl group;

R³ represents

an optionally substituted C₁-C₁₈ alkyl group, preferably an optionallysubstituted C₁-C₆ alkyl group, more preferably a C₁-C₄ alkyl group, suchas methyl, ethyl, propyl, isopropyl, butyl, isobutyl and t-butyl,

an optionally substituted lower alkenyl group, or

an optionally substituted lower alkoxy group; or

R² and R³ together represent —(CH₂)m— in which m is 3 or 4; and

W represents 1 to 4 substituents on the nucleus which may be identicalor different and each of which is

a halogen atom,

an optionally substituted C₁-C₁₀ alkyl group,

an optionally substituted lower alkenyl group,

an optionally substituted lower alkynyl group,

an optionally substituted C₁-C₁₀ alkoxy group,

an optionally substituted C₃-C₁₀ cycloalkyl group,

an optionally substituted aryl group,

an optionally substituted aryloxy group,

NR⁸R⁹ in which R⁸ and R⁹ are each a hydrogen atom, an optionallysubstituted C₁-C₆ alkyl group or an optionally substituted phenyl group,or R⁸ and R⁹ together with N may form a four- to six-membered ringcontaining one or two heteroatoms,

COR¹⁰ in which R¹⁰ is a hydrogen atom, an optionally substituted loweralkyl group or an optionally substituted lower alkenyl group,

COOR¹¹ in which R¹¹ is a hydrogen atom, an optionally substituted loweralkyl group or an optionally substituted lower alkenyl group,

a nitro group, or

a cyano group.

Agriculturally and horticulturally acceptable acid addition salts of the4-quinolinol derivative represented by the aforementioned generalformula (I) mean salts generally usable in agriculture and horticulture,such as hydrochloride, nitrate, sulfate, phosphate and acetate.

The 4-quinolinol derivative represented by the aforementioned generalformula (I) may be in the form of hydrate or solvate. Such hydrate andsolvate of the compound represented by the general formula (I) are alsoincluded in the present invention.

Substituents which optionally present on the 4-quinoline derivativerepresented by the aforementioned general formula (I) include a halogenatom, such as fluorine, bromine and chlorine, a C₁-C₄ alkyl group, aC₁-C₄ alkoxy group, a hydroxyl group, a nitro group, a formyl group, acyano group and the like.

The term “lower alkyl group” as used herein means an alkyl groupcontaining about 1 to 4 carbon atoms, such as methyl, ethyl, propyl orbutyl.

The term “lower alkenyl group” as used herein means an alkenyl groupcontaining about 2 to 4 carbon atoms, such as vinyl, (1- or 2-)propenylor (1-, 2- or 3-)butenyl.

The term “lower alkynyl group” as used herein means an alkynyl groupcontaining about 2 to 4 carbon atoms, such as ethynyl, (1- or2-)propynyl or (1-, 2- or 3-)butynyl.

The term “lower alkoxy group” as used herein means an alkoxy groupcontaining about 1 to 4 carbon atoms, such as methoxy, ethoxy, propyloxyor butyloxy.

The term “C₁-C₁₈ alkyl group” as used herein means an alkyl group, suchas methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl or octadecyl.

The term “C₂-C₁₈ alkenyl group” as used herein means, for example,vinyl, (1- or 2-)propenyl, (1-, 2- or 3-)butenyl, (1-, 2-, 3- or4-)pentenyl, (1-, 2-, 3-, 4- or 5-)hexenyl, (1-, 2-, 3-, 4-, 5- or6-)heptenyl, (1-, 2-, 3-, 4-, 5-, 6- or 7-)octenyl, (1-, 2-, 3-, 4-, 5-,6-, 7- or 8-)nonenyl, (1-, 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-)decenyl,(1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-)undecenyl, (1-, 2-, 3-, 4-,5-, 6-, 7-, 8-, 9-, 10- or 11-)dodecenyl, (1-, 2-, 3-, 4-, 5-, 6-, 7-,8-, 9-, 10-, 11- or 12-)tridecenyl, (1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-,10-, 11-, 12- or 13-)tetradecenyl, (1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-,10-, 11-, 12-, 13- or 14-)pentadecenyl, (1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-,9-, 10-, 11-, 12-, 13-, 14- or 15-)hexadecenyl, (1-, 2-, 3-, 4-, 5-, 6-,7-, 8-, 9-, 10-, 11-, 12-, 13-, 14-, 15- or 16-)heptadecenyl, or (1-,2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12-, 13-, 14-, 15-, 16- or17-)octadecenyl.

The term “C₃-C₁₀ cycloalkyl group” as used herein means, for example,cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl,cyclooctyl, cyclononyl or cyclodecyl.

The term “C₁-C₁₀ alkoxy group” as used herein means, for example,methoxy, ethoxy, propyloxy, butyloxy, pentyloxy, hexyloxy, heptyloxy,octyloxy, nonyloxy or decyloxy.

The term “phenyl lower alkyl group” as used herein means a phenylalkylgroup having a C₁-C₄ alkyl moiety, such as benzyl, (1- or2-)phenylethyl, (1-, 2- or 3-)phenylpropyl or (1-, 2-, 3- or4-)phenylbutyl.

The term “phenoxy lower alkyl group” as used herein means a phenoxyalkylgroup having a C₁-C₄ alkyl moiety, such as phenoxymethyl, (1- or2-)phenoxyethyl, (1-, 2- or 3-)phenoxypropyl or (1-, 2-, 3- or4-)phenoxybutyl.

The following Table 1 specifically illustrates the compounds within thescope of the 4-hydroxyquinoline derivatives represented by the generalformula (I) of the present invention.

Abbreviations used in Table 1 and Examples have following meanings.

TABLE 1 iso-C₃H₇ isopropyl t-C₄H₉ tertiary butyl s-C₄H₉ secondary butylc-C₅H₉ cyclopentyl c-C₆H₁₁ cyclohexyl n-pentyl normal pentyl com- poundNo. R¹ R² R³ W  1 H CH₃ CH₃ 6-CH₃  2 CH₃CO CH₃ CH₃ 6-CH₃  3 C₆H₅CO CH₃CH₃ 6-CH₃  4 CH₃OCO CH₃ CH₃ 6-CH₃  5 H CH₃ CH₃ 6-CH₃O  6 CH₃CO CH₃ CH₃6-CH₃O  7 C₆H₅CO CH₃ CH₃ 6-CH₃O  8 CH₃OCO CH₃ CH₃ 6-CH₃O  9 H CH₃ CH₃6-C₂H₅  10 CH₃CO CH₃ CH₃ 6-C₂H₅  11 C₆H₅CO CH₃ CH₃ 6-C₂H₅  12 CH₃OCO CH₃CH₃ 6-C₂H₅  13 H CH₃ CH₃ 6-C₃H₇  14 CH₃CO CH₃ CH₃ 6-C₃H₇  15 C₆H₅CO CH₃CH₃ 6-C₃H₇  16 CH₃OCO CH₃ CH₃ 6-C₃H₇  17 (C₂H₅)₂NCO CH₃ CH₃ 6-C₃H₇  18 HCH₃ CH₃ 6-iso-C₃H₇  19 CH₃CO CH₃ CH₃ 6-iso-C₃H₇  20 C₆H₅CO CH₃ CH₃6-iso-C₃H₇  21 CH₃OCO CH₃ CH₃ 6-iso-C₃H₇  22 (C₂H₅)₂NCO CH₃ CH₃6-iso-C₃H₇  23 H CH₃ CH₃ 6-iso-C₃H₇O  24 CH₃CO CH₃ CH₃ 6-iso-C₃H₇O  25C₆H₅CO CH₃ CH₃ 6-iso-C₃H₇O  26 CH₃OCO CH₃ CH₃ 6-iso-C₃H₇O  27 C₆H₅OCOCH₃ CH₃ 6-iso-C₃H₇O  28 H CH₃ CH₃ 6-C₄H₉  29 CH₃CO CH₃ CH₃ 6-C₄H₉  30C₂H₅CO CH₃ CH₃ 6-C₄H₉  31 c-C₃H₅CO CH₃ CH₃ 6-C₄H₉  32 t-C₄H₉CO CH₃ CH₃6-C₄H₉  33 C₆H₅CO CH₃ CH₃ 6-C₄H₉  34 4-CH₃O—C₆H₄CO CH₃ CH₃ 6-C₄H₉  354-Cl—C₆H₄CO CH₃ CH₃ 6-C₄H₉  36 CH₃OCO CH₃ CH₃ 6-C₄H₉  37 C₂H₅OCO CH₃ CH₃6-C₄H₉  38 C₈H₁₇OCO CH₃ CH₃ 6-C₄H₉  39 C₆H₅OCO CH₃ CH₃ 6-C₄H₉  404-CH₃O—C₆H₄CO CH₃ CH₃ 6-C₄H₉  41 4-Cl-C₆H₄OCO CH₃ CH₃ 6-C₄H₉  42 (C₂H₅₎₂NCO CH₃ CH₃ 6-C₄H₉  43 (C₆H₅₎ ₂NCO CH₃ CH₃ 6-C₄H₉  44 CH₃CO C₂H₅ CH₃6-C₄H₉  45 CH₃CO C₃H₇ CH₃ 6-C₄H₉  46 CH₃CO C₄H₉ CH₃ 6-C₄H₉  47 CH₃CO CH₃C₂H₅ 6-C₄H₉  48 CH₃CO CH₃ C₃H₇ 6-C₄H₉  49 CH₃CO CH₃ C₄H₉ 6-C₄H₉  50 H—(CH₂)₄— 6-C₄H₉  51 CH₃CO —(CH₂)₄— 6-C₄H₉  52 C₂H₅CO —(CH₂)₄— 6-C₄H₉  53C₆H₅CO —(CH₂)₄— 6-C₄H₉  54 H CH₃ CH₃ 6-s-C₄H₉  55 CH₃CO CH₃ CH₃ 6-s-C₄H₉ 56 C₂H₅CO CH₃ CH₃ 6-s-C₄H₉  57 c-C₃H₅CO CH₃ CH₃ 6-s-C₄H₉  58 t-C₄H₉COCH₃ CH₃ 6-s-C₄H₉  59 t-C₄H₉CH₂CO CH₃ CH₃ 6-s-C₄H₉  60 C₈H₁₇CO CH₃ CH₃6-s-C₄H₉  61 C₆H₅CO CH₃ CH₃ 6-s-C₄H₉  62 4-CH₃O—C₆H₄CO CH₃ CH₃ 6-s-C₄H₉ 63 4-Cl—C₆H₄CO CH₃ CH₃ 6-s-C₄H₉  64 2,6-di-CH₃O—C₆H₃CO CH₃ CH₃ 6-s-C₄H₉ 65 CH₃OCO CH₃ CH₃ 6-s-C₄H₉  66 C₂H₅OCO CH₃ CH₃ 6-s-C₄H₉  67 C₈H₁₇OCOCH₃ CH₃ 6-s-C₄H₉  68 C₆H₅OCO CH₃ CH₃ 6-s-C₄H₉  69 4-CH₃O—C₆H₄OCO CH₃ CH₃6-s-C₄H₉  70 4-Cl—C₆H₄OCO CH₃ CH₃ 6-s-C₄H₉  71 (CH₃)₂NCO CH₃ CH₃6-s-C₄H₉  72 (C₂H₅)₂NCO CH₃ CH₃ 6-s-C₄H₉  73 CH₃(C₆H₅)NCO CH₃ CH₃6-s-C₄H₉  74 (C₆H₅)₂NCO CH₃ CH₃ 6-s-C₄H₉  75 H CH₃ CH₃O 6-t-C₄H₉  76CH₃CO CH₃ CH₃O 6-t-C₄H₉  77 H CH₃ CH₃O 6-s-C₄H₉  78 CH₃CO CH₃ CH₃O6-s-C₄H₉  79 CH₃CO CH₃ CF₃ 6-s-C₄H₉  80 H CH₃ CF₃ 6-s-C₄H₉  81 CH₃CO CH₃CF₃ 6-t-C₄H₉  82 H CH₃ CF₃ 6-t-C₄H₉  83 H CH₃ CH₃ 6-t-C₄H₉  84 CH₃CO CH₃CH₃ 6-t-C₄H₉  85 C₂H₅CO CH₃ CH₃ 6-t-C₄H₉  86 c-C₃H₅CO CH₃ CH₃ 6-t-C₄H₉ 87 C₆H₅CO CH₃ CH₃ 6-t-C₄H₉  88 CH₃OCO CH₃ CH₃ 6-t-C₄H₉  89 C₂H₅OCO CH₃CH₃ 6-t-C₄H₉  90 C₆H₅OCO CH₃ CH₃ 6-t-C₄H₉  91 (C₂H₅)₂NCO CH₃ CH₃6-t-C₄H₉  92 H CH₃ CH₃ 6-iso-C₄H₉  93 CH₃CO CH₃ CH₃ 6-iso-C₄H₉  94C₆H₅CO CH₃ CH₃ 6-iso-C₄H₉  95 CH₃OCO CH₃ CH₃ 6-iso-C₄H₉  96 C₆H₅OCO CH₃CH₃ 6-iso-C₄H₉  97 H CH₃ CH₃ 6-C₅H₁₁  98 CH₃CO CH₃ CH₃ 6-C₅H₁₁  99C₆H₅CO CH₃ CH₃ 6-C₅H₁₁ 100 CH₃OCO CH₃ CH₃ 6-C₅H₁₁ 101 C₆H₅OCO CH₃ CH₃6-C₅H₁₁ 102 H CH₃ CH₃ 6-c-C₅H₉ 103 CH₃CO CH₃ CH₃ 6-c-C₅H₉ 104 C₆H₅CO CH₃CH₃ 6-c-C₅H₉ 105 CH₃OCO CH₃ CH₃ 6-c-C₅H₉ 106 (C₂H₅)₂NCO CH₃ CH₃ 6-c-C₅H₉107 H CH₃ CH₃ 6-C₆H₁₃ 108 CH₃CO CH₃ CH₃ 6-C₆H₁₃ 109 C₆H₅CO CH₃ CH₃6-C₆H₁₃ 110 CH₃OCO CH₃ CH₃ 6-C₆H₁₃ 111 H CH₃ CH₃ 6-c-C₆H₁₁ 112 CH₃CO CH₃CH₃ 6-c-C₆H₁₁ 113 C₂H₅CO CH₃ CH₃ 6-c-C₆H₁₁ 114 C₆H₅CO CH₃ CH₃ 6-c-C₆H₁₁115 4-CH₃O—C₆H₄CO CH₃ CH₃ 6-c-C₆H₁₁ 116 4-Cl—C₆H₄CO CH₃ CH₃ 6-c-C₆H₁₁117 CH₃OCO CH₃ CH₃ 6-c-C₆H₁₁ 118 C₆H₅CO CH₃ CH₃ 6-c-C₆H₁₁ 119 (C₂H₅)₂NCOCH₃ CH₃ 6-c-C₆H₁₁ 120 H CH₃ CH₃ 6-C₇H₁₅ 121 CH₃CO CH₃ CH₃ 6-C₇H₁₅ 122C₆H₅CO CH₃ CH₃ 6-C₇H₁₅ 123 CH₃OCO CH₃ CH₃ 6-C₇H₁₅ 124 C₆H₅OCO CH₃ CH₃6-C₇H₁₅ 125 H CH₃ CH₃ 6-C₈H₁₇ 126 CH₃CO CH₃ CH₃ 6-C₈H₁₇ 127 C₆H₅CO CH₃CH₃ 6-C₈H₁₇ 128 CH₃OCO CH₃ CH₃ 6-C₈H₁₇ 129 C₂H₅OCO CH₃ CH₃ 6-C₈H₁₇ 130C₆H₅OCO CH₃ CH₃ 6-C₈H₁₇ 131 H CH₃ CH₃ 6-CF₃ 132 CH₃CO CH₃ CH₃ 6-CF₃ 133C₆H₅CO CH₃ CH₃ 6-CF₃ 134 CH₃OCO CH₃ CH₃ 6-CF₃ 135 H CH₃ CH₃ 6-C₆H₅O 136CH₃CO CH₃ CH₃ 6-C₆H₅O 137 C₆H₅CO CH₃ CH₃ 6-C₆H₅O 138 H CH₃ CH₃ 5-C₂H₅139 H CH₃ CH₃ 5-C₃H₇ 140 H CH₃ CH₃ 7-C₂H₅ 141 H CH₃ CH₃ 7-C₃H₇ 142 H CH₃CH₃ 8-C₂H₅ 143 H CH₃ CH₃ 8-C₃H₇ 144 H CH₃ CH₃ 6-C₄H₉, 8-CH₃ 145 CH₃COCH₃ CH₃ 6-C₄H₉, 8-CH₃ 146 H CH₃ CH₃ 6-C₄H₉, 8-F 147 CH₃CO CH₃ CH₃6-C₄H₉, 8-F 148 H CH₃ CH₃ 6-C₄H₉, 7-CH₃ 149 CH₃CO CH₃ CH₃ 6-C₄H₉, 7-CH₃150 H CH₃ CH₃ 6-C₄H₉, 7-F 151 CH₃CO CH₃ CH₃ 6-C₄H₉, 7-F 152 H —(CH₂)₃—6-s-C₄H₉ 153 CH₃CO —(CH₂)₃— 6-s-C₄H₉ 154 H CH₃ CH₃ 6-N(CH₂CH₃)₂ 155CH₃CO CH₃ CH₃ 6-N(CH₂CH₃₎ ₂ 156 H CH₃ CH₃ 6-Morpholino 157 CH₃CO CH₃ CH₃6-Morpholino 158 H —(CH₂)₄— 6-iso-C₄H₉ 159 CH₃CO —(CH₂)₄— 6-iso-C₄H₉ 160C₂H₅CO —(CH₂)₄— 6-iso-C₄H₉ 161 C₆H₅CO —(CH₂)₄— 6-iso-C₄H₉ 162 H —(CH₂)₄—6-s-C₄H₉ 163 CH₃CO —(CH₂)₄— 6-s-C₄H₉ 164 C₂H₅CO —(CH₂)₄— 6-s-C₄H₉ 165C₆H₅CO —(CH₂)₄— 6-s-C₄H₉ 166 H —(CH₂)₄— 6-N(CH₃)₂ 167 CH₃CO —(CH₂)_(4—)6-N(CH₃)₂ 168 C₂H₅CO —(CH₂)₄— 6-N(CH₃)₂ 169 C₆H₅CO —(CH₂)₄— 6-N(CH₃)₂170 c-C₆H₁₁CO CH₃ CH₃ 6-s-C₄H₉ 171 4-NO₂—C₆H₄CO CH₃ CH₃ 6-s-C₄H₉ 172C₆H₅CH₂CO CH₃ CH₃ 6-s-C₄H₉ 173 C₅H₁₁CO CH₃ CH₃ 6-s-C₄H₉ 174 C₆H₁₃CO CH₃CH₃ 6-s-C₄H₉ 175 CH₂═CHCH₂CO CH₃ CH₃ 6-s-C₄H₉ 176 iso-C₄H₉CO CH₃ CH₃6-s-C₄H₉ 177 2,6-diCl—C₆H₃CO CH₃ CH₃ 6-s-C₄H₉ 178 H CH₃ CH₃6-(1-c-pentenyl) 179 C₄H₉OCO CH₃ CH₃ 6-s-C₄H₉ 180 C₇H₁₅CO CH₃ CH₃6-s-C₄H₉ 181 H CH₃ CH₃ 6-Br 182 CH₃CO CH₃ CH₃ 5-C₂H₅ 183 CH₃CO CH₃ CH₃7-C₂H₅ 184 CH₃CO CH₃ CH₃ 8-C₂H₅ 185 CH₃CO CH₃ CH₃ 6-Br 186 H CH₃ CH₃6-C₄H₉, 8-Br 187 CH₃CO CH₃ CH₃ 6-C₄H₉, 8-Br 188 H CH₃ C₈H₁₇ 6-s-C₄H₉ 189CH₃CO CH₃ C₈H₁₇ 6-s-C₄H₉ 190 H CH₃ CH₃ 6-Br, 8-CH₃ 191 H CH₃ CH₃ 5-CH₃,6-Br 192 H CH₃ CH₃ 6-Br, 7-CH₃ 193 H CH₃ CH₃ 6-Br, 8-F 194 H CH₃ CH₃6-F, 8-CH₃ 195 CH₃CO CH₃ CH₃ 6-Br, 8-CH₃ 196 CH₃CO CH₃ CH₃ 6-Br, 7-CH₃197 CH₃CO CH₃ CH₃ 5-CH₃, 6-Br 198 CH₃CO CH₃ CH₃ 6-F, 8-CH₃ 199 H CH₃ CH₃6-CH₃CH═C(CH₃) 200 CH₃CO CH₃ CH₃ 6-CH₃CH═C(CH₃) 201 H CH₃ CH₃ 5-CH₃,6-s-C₄H₉ 202 CH₃CO CH₃ CH₃ 5-CH₃, 6-s-C₄H₉ 203 H CH₃ CH₃ 6-s-C₄H₉, 7-CH₃204 CH₃CO CH₃ CH₃ 6-s-C₄H₉, 7-CH₃ 205 H CH₃ CH₃ 6-s-C₄H₉, 8-CH₃ 206CH₃CO CH₃ CH₃ 6-s-C₄H₉, 8-CH₃ 207 H CH₃ CH₃ 5-F, 6-s-C₄H₉ 208 CH₃CO CH₃CH₃ 5-F, 6-s-C₄H₉ 209 H CH₃ CH₃ 6-s-C₄H₉, 7-F 210 CH₃CO CH₃ CH₃6-s-C₄H₉, 7-F 211 H CH₃ CH₃ 6-s-C₄H₉, 8-F 212 CH₃CO CH₃ CH₃ 6-s-C₄H₉,8-F 213 H CH₃ CH₃ 6-s-C₄H₉, 8-Cl 214 CH₃CO CH₃ CH₃ 6-s-C₄H₉, 8-Cl 215 HCH₃ CH₃ 6-n-C₄H₉, 8-Cl 216 CH₃CO CH₃ CH₃ 6-n-C₄H₉, 8-Cl 217 H CH₃ CH₃6-t-C₄H₉, 8-Cl 218 CH₃CO CH₃ CH₃ 6-t-C₄H₉, 8-Cl 219 H CH₃ CH₃ 6-s-C₄H₉,8-CH₃O 220 CH₃CO CH₃ CH₃ 6-s-C₄H₉, 8-CH₃O 221 H CH₃ CH₃ 6-n-C₄H₉, 8-CH₃O222 CH₃CO CH₃ CH₃ 6-n-C₄H₉, 8-CH₃O 223 H CH₃ CH₃ 6-t-C₄H₉, 8-CH₃O 224CH₃CO CH₃ CH₃ 6-t-C₄H₉, 8-CH₃O 225 H CH₃ CH₃ 6-s-C₄H₉, 5-Cl 226 CH₃COCH₃ CH₃ 6-s-C₄H₉, 5-Cl 227 H CH₃ CH₃ 6-t-C₄H₉, 5-Cl 228 CH₃CO CH₃ CH₃6-t-C₄H₉, 5-Cl 229 H CH₃ CH₃ 6-n-C₄H₉, 5-Cl 230 CH₃CO CH₃ CH₃ 6-n-C₄H₉,5-Cl 231 H CH₃ CH₃ 6-s-C₄H₉, 5-CH₃O 232 CH₃CO CH₃ CH₃ 6-s-C₄H₉, 5-CH₃O233 H CH₃ CH₃ 6-n-C₄H₉, 5-CH₃O 234 CH₃CO CH₃ CH₃ 6-n-C₄H₉, 5-CH₃O 235 HCH₃ CH₃ 6-t-C₄H₉, 5-OCH₃ 236 CH₃CO CH₃ CH₃ 6-t-C₄H₉, 5-OCH₃ 237 H CH₃CH₃ 6-s-C₄H₉, 7-Cl 238 CH₃CO CH₃ CH₃ 6-s-C₄H₉, 7-Cl 239 H CH₃ CH₃6-t-C₄H₉, 7-Cl 240 CH₃CO CH₃ CH₃ 6-t-C₄H₉, 7-Cl 241 H CH₃ CH₃ 6-n-C₄H₉,7-Cl 242 CH₃CO CH₃ CH₃ 6-n-C₄H₉, 7-Cl 243 H CH₃ CH₃ 6-s-C₄H₉, 7-CH₃O 244CH₃CO CH₃ CH₃ 6-s-C₄H₉, 7-CH₃O 245 H CH₃ CH₃ 6-n-C₄H₉, 7-CH₃O 246 CH₃COCH₃ CH₃ 6-n-C₄H₉, 7-CH₃O 247 H CH₃ CH₃ 6-t-C₄H₉, 7-CH₃O 248 CH₃CO CH₃CH₃ 6-t-C₄H₉, 7-CH₃O 249 H CH₃ CH₃ 6-t-C₄H₉, 8-CH₃ 250 CH₃CO CH₃ CH₃6-t-C₄H₉, 8-CH₃ 251 H CH₃ CH₃ 6-t-C₄H₉, 8-F 252 CH₃CO CH₃ CH₃ 6-t-C₄H₉,8-F 253 H CH₃ CH₃ 6-t-C₄H₉, 5-CH₃ 254 CH₃CO CH₃ CH₃ 6-t-C₄H₉, 5-CH₃ 255H CH₃ CH₃ 6-t-C₄H₉, 5-F 256 CH₃CO CH₃ CH₃ 6-t-C₄H₉, 5-F 257 H CH₃ CH₃6-t-C₄H₉, 7-CH₃ 258 CH₃CO CH₃ CH₃ 6-t-C₄H₉, 7-CH₃ 259 H CH₃ CH₃6-t-C₄H₉, 7-F 260 CH₃CO CH₃ CH₃ 6-t-C₄H₉, 7-F 261 H CH₃ CH₃ 6-CH₃, 8-CH₃262 CH₃CO CH₃ CH₃ 6-CH₃, 8-CH₃ 263 H CH₃ CH₃ 5-CH₃, 6-CH₃ 264 CH₃CO CH₃CH₃ 5-CH₃, 6-CH₃ 265 H CH₃ CH₃ 6-CH₃, 7-CH₃ 266 CH₃CO CH₃ CH₃ 6-CH₃,7-CH₃ 267 H CH₃ CH₃ 6-C₂H₅, 8-C₂H₅ 268 CH₃CO CH₃ CH₃ 6-C₂H₅, 8-C₂H₅ 269H CH₃ CH₃ 5-C₂H₅, 6-C₂H₅ 270 CH₃CO CH₃ CH₃ 5-C₂H₅, 6-C₂H₅ 271 H CH₃ CH₃6-C₂H₅, 7-C₂H₅ 272 CH₃CO CH₃ CH₃ 6-C₂H₅, 7-C₂H₅ 273 H CH₃ CH₃6-iso-C₃H₇, 8-iso-C₃H₇ 274 CH₃CO CH₃ CH₃ 6-iso-C₃H₇, 8-iso-C₃H₇ 275 HCH₃ CH₃ 5-iso-C₃H₇, 6-iso-C₃H₇ 276 CH₃CO CH₃ CH₃ 5-iso-C₃H₇, 6-iso-C₃H₇277 H CH₃ CH₃ 6-iso-C₃H₇, 7-iso-C₃H₇, 278 CH₃CO CH₃ CH₃ 6-iso-C₃H₇,7-iso-C₃H₇, 279 H CH₃ CH₃ 6-s-C₄H₉, 8-s-C₄H₉ 280 CH₃CO CH₃ CH₃ 6-s-C₄H₉,8-s-C₄H₉ 281 H CH₃ CH₃ 5-s-C₄H₉, 6-s-C₄H₉ 282 CH₃CO CH₃ CH₃ 5-s-C₄H₉,6-s-C₄H₉ 283 H CH₃ CH₃ 6-s-C₄H₉, 7-s-C₄H₉ 284 CH₃CO CH₃ CH₃ 6-s-C₄H₉,7-s-C₄H₉ 285 H CH₃ CH₃ 6-t-C₄H₉, 8-t-C₄H₉ 286 CH₃CO CH₃ CH₃ 6-t-C₄H₉,8-t-C₄H₉ 287 H CH₃ CH₃ 5-t-C₄H₉, 6-t-C₄H₉ 288 CH₃CO CH₃ CH₃ 5-t-C₄H₉,6-t-C₄H₉ 289 H CH₃ CH₃ 6-t-C₄H₉, 7-t-C₄H₉ 290 CH₃CO CH₃ CH₃ 6-t-C₄H₉,7-t-C₄H₉ 291 H CH₃ CH₃ 6-c-C₃H₄(CH₃) 292 CH₃CO CH₃ CH₃ 6-c-C₃H₄(CH₃) 293H CH₃ CH₃ 6-c-C₃H₄(CH₃), 8-CH₃ 294 CH₃CO CH₃ CH₃ 6-c-C₃H₄(CH₃), 8-CH₃295 H CH₃ CH₃ 6-c-C₃H₄(CH₃), 8-Cl 296 CH₃CO CH₃ CH₃ 6-c-C₃H₄(CH₃), 8-Cl297 H CH₃ CH₃ 6-c-C₃H₅—CH₂ 298 CH₃CO CH₃ CH₃ 6-c-C₃H₅—CH₂ 299 H CH₃ CH₃6-c-C₃H₅—CH₂, 8-CH₃ 300 CH₃CO CH₃ CH₃ 6-c-C₃H₅—CH₂, 8-CH₃ 301 H CH₃ CH₃6-c-C₃H₅—CH₂, 8-Cl 302 CH₃CO CH₃ CH₃ 6-c-C₃H₅—CH₂, 8-Cl 303 H CH₃ CH₃6-C₆H₅ 304 CH₃CO CH₃ CH₃ 6-C₆H₅ 305 H CH₃ CH₃ 6-C₆H₅, 8-CH₃ 306 CH₃COCH₃ CH₃ 6-C₆H₅, 8-CH₃ 307 H CH₃ CH₃ 6-C₆H₅, 8-Cl 308 CH₃CO CH₃ CH₃6-C₆H₅, 8-Cl 309 H CH₃ CH₃ 6-(p-Cl)—C₆H₄ 310 CH₃CO CH₃ CH₃ 6-(p-Cl)—C₆H₄311 H CH₃ CH₃ 6-(p-Cl)—C₆H₄, 8-CH₃ 312 CH₃CO CH₃ CH₃ 6-(p-Cl)—C₆H₄,8-CH₃ 313 H CH₃ CH₃ 6-(p-Cl)—C₆H₄, 8-Cl 314 CH₃CO CH₃ CH₃ 6-(p-Cl)—C₆H₄,8-Cl 315 H CH₃ CH₃ 6-(p-CH₃)—C₆H₄ 316 CH₃CO CH₃ CH₃ 6-(p-CH₃)—C₆H₄ 317 HCH₃ CH₃ 6-(p-CH₃)—C₆H₄, 8-CH₃ 318 CH₃CO CH₃ CH₃ 6-(p-CH₃)—C₆H₄, 8-CH₃319 H CH₃ CH₃ 6-(p-CH₃)—C₆H₄, 8-Cl 320 CH₃CO CH₃ CH₃ 6-(p-CH₃)—C₆H₄,8-Cl 321 H CH₃ CH₃ 6-C₆H₅—CH₂ 322 CH₃CO CH₃ CH₃ 6-C₆H₅CH₂ 323 H CH₃ CH₃6-C₆H₅—CH₂, 8-CH₃ 324 CH₃CO CH₃ CH₃ 6-C₆H₅—CH₂, 8-CH₃ 325 H CH₃ CH₃6-C₆H₅—CH₂, 8-Cl 326 CH₃CO CH₃ CH₃ 6-C₆H₅—CH₂, 8-Cl 327 H CH₃ CH₃6-C₆H₅—C(CH₃)₂ 328 CH₃CO CH₃ CH₃ 6-C₆H₅—C(CH₃)₂ 329 H CH₃ CH₃6-C₆H₅—C(CH₃)_(2,) 8-CH₃ 330 CH₃CO CH₃ CH₃ 6-C₆H₅—C(CH₃)₂, 8-CH₃ 331 HCH₃ CH₃ 6-C₆H₅—C(CH₃)₂, 8-Cl 332 CH₃CO CH₃ CH₃ 6-C₆H₅—C(CH₃)₂, 8-Cl 333H CH₃ CH₃ 6-t-C₄H₉—C₂ 334 CH₃CO CH₃ CH₃ 6-t-C₄H₉—CH₂ 335 H CH₃ CH₃6-t-C₄H₉—CH₂, 8-CH₃ 336 CH₃CO CH₃ CH₃ 6-t-C₄H₉—CH₂, 8-CH₃ 337 H CH₃ CH₃6-t-C₄H₉—CH₂, 8-Cl 338 CH₃CO CH₃ CH₃ 6-t-C₄H₉—CH₂, 8-Cl 339 H CH₃ CH₃6-s-C₄H₉, 8-CH₂OH 340 CH₃CO CH₃ CH₃ 6-s-C₄H₉, 8-CH₂OH 341 H CH₃ CH₃6-t-C₄H₉, 8-CH₂OH 342 CH₃CO CH₃ CH₃ 6-t-C₄H₉ _(,) 8-CH₂OH 343 H CH₃ CH₃6-s-C₄H₉, 8-CH₂Cl 344 CH₃CO CH₃ CH₃ 6-s-C₄H₉, 8-CH₂Cl 345 H CH₃ CH₃6-t-C₄H₉, 8-CH₂Cl 346 CH₃CO CH₃ CH₃ 6-t-C₄H₉, 8-CH₂Cl 347 H CH₃ CH₃6-s-C₄H₉, 8-C₂H₅ 348 CH₃CO CH₃ CH₃ 6-s-C₄H₉, 8-C₂H₅ 349 H CH₃ CH₃6-t-C₄H₉, 8-C₂H₅ 350 CH₃CO CH₃ CH₃ 6-t-C₄H₉, 8-C₂H₅ 351 H CH₃ CH₃6-c-C₅H₉, 8-CH₃ 352 CH₃CO CH₃ CH₃ 6-c-C₅H₉, 8-CH₃ 353 H CH₃ CH₃6-c-C₅H₉, 8-Cl 354 CH₃CO CH₃ CH₃ 6-c-C₅H₉, 8-Cl 355 H CH₃ CH₃ 6-s-C₄H₉,8-CHO 356 CH₃CO CH₃ CH₃ 6-s-C₄H₉, 8-CHO 357 H CH₃ CH₃ 6-t-C₄H₉, 8-CHO358 CH₃CO CH₃ CH₃ 6-t-C₄H₉, 8-CHO 359 H CH₃ CH₃ 6-CH₃CH═C(CH₃), 8-CH₃360 CH₃CO CH₃ CH₃ 6-CH₃CH═C(CH₃), 8-CH₃ 361 H CH₃ CH₃ 6-CH₃CH═C(CH₃),8-F 362 CH₃CO CH₃ CH₃ 6-CH₃CH═C(CH₃), 8-F 363 H CH₃ CH₃ 6-s-C₄H₉, 8-CN364 CH₃CO CH₃ CH₃ 6-s-C₄H₉, 8-CN 365 H CH₃ CH₃ 6-t-C₄H₉, 8-CN 366 CH₃COCH₃ CH₃ 6-t-C₄H₉, 8-CN 367 H CH₃ CH₃ 6-s-C₄H₉, 8-NO₂ 368 CH₃CO CH₃ CH₃6-s-C₄H₉, 8-NO₂ 369 H CH₃ CH₃ 6-t-C₄H₉, 8-NO₂ 370 CH₃CO CH₃ CH₃6-t-C₄H₉, 8-NO₂ 371 H CH₃ CH₃ 6-s-C₄H₉, 8-CH₃OCO 372 CH₃CO CH₃ CH₃6-s-C₄H₉, 8-CH₃OCO 373 H CH₃ CH₃ 6-t-C₄H₉, 8-CH₃OCO 374 CH₃CO CH₃ CH₃6-t-C₄H_(9,) 8-CH₃OCO

Compounds of the general formula (I)′ which comprise a part of4-quinolinol derivatives represented by the general formula (I) can beprepared by the known method as described in JP-03128355A according tothe following scheme.

Thus, a compound of the general formula (I)′ was synthesized by reactinga compound represented by the general formula (II) with a reagentrepresented by the general formula (III) or (IV) in the presence orabsence of a base and by, if necessary, replacing a substituent of thethus obtained compound with a desired substituent. In the aboveformulae, R¹ to R⁴ and W are as defined above. Example of the usablebase includes organic amines, such as triethylamine and pyridine, orinorganic alkalis, such as sodium carbonate, potassium carbonate andsodium hydride. A compound of the general formula (II) as one of thestarting materials was synthesized by a known method as described in J.Am. Chem. Soc., 70, 2402 (1948); Tetrahedron Lett., 27, 5323 (1986)using as a starting material, a substituted aniline which wascommercially available or prepared by a known method. And, the reagentrepresented by the general formula (III) or (IV) is desirably used in anamount of 1 to 50 equivalents, preferably 1 to 10 equivalents withrespect to the compound of the general formula (II). The reaction can becarried out in an inert organic solvent, such as dimethylformamide ordimethyl sulfoxide, at the temperature ranging from 0 to 140° C.

Compounds represented by the aforementioned general formula (I) have anexcellent fungicidal effect against blast of rice, brown spot of rice,powdery mildew of Cucurbitaceae, anthracnose of potato and the like.

When the present compound represented by the general formula (I) is usedas an active ingredient of an agricultural and horticultural fungicide,it can be used as such. However, the present compound is generally usedin any formulation, such as emulsifiable concentrate, solution, wettablepowder, dust formulation, granule, oil solution, aerosol or flowable,which is prepared by combining the present compound with suitableadjuvants, such as solid carrier, liquid carrier, gaseous carrier,surfactant, dispersant and other additives.

Example of the solid carrier includes talc, bentonite, clay, kaolin,diatomaceous earth, vermiculite, white carbon, calcium carbonate and thelike. Example of the liquid carrier includes alcohols, such as methanol,n-hexanol and ethylene glycol; ketones, such as acetone, methyl ethylketone and cyclohexanone; aliphatic hydrocarbons, such as n-hexane,kerosine and kerosene; aromatic hydrocarbons, such as toluene, xyleneand methylnaphthalene; ethers, such as diethyl ether, dioxane andtetrahydrofuran; esters, such as ethyl acetate; nitrites, such asacetonitrile and isobutyronitrile; acid amides, such asdimethylformamide and dimethylacetamide; vegetable oils, such as soybeanoil and cottonseed oil; dimethyl sulfoxide; water; and the like. And,example of the gaseous carrier includes LPG, air, nitrogen, carbondioxide gas, dimethyl ether and the like.

Example of the surfactant or dispersant used for emulsification,dispersion and wetting includes alkyl sulfate esters, alkyl(aryl)sulfonate salts, polyoxyalkylene alkyl(aryl) ethers, polyhydric alcoholesters, lignin sulfonate salts and the like.

And, example of the adjuvant used for improving properties of aformulation includes carboxymethylcellulose, gum arabic, polyethyleneglycol, calcium stearate and the like.

The above carrier, surfactant, dispersant and adjuvant may be used aloneor in combination, if necessary.

Suitable amount of the active ingredient is generally 1 to 75% by weightin emulsifiable concentrate, generally 0.3 to 25% by weight in dustformulation, generally 1 to 90% by weight in wettable powder, orgenerally 0.5 to 10% by weight in granule.

Each of these formulations may be used as such or after dilution.Further, each of these formulations may be used in admixture with anyother fungicide, insecticide, acaricide, herbicide, plant growthregulator, fertilizer and the like.

The application methods of the agricultural and horticultural fungicideof the present invention includes foliar application, paddy waterapplication, soil treatment, nursery box application, seed disinfectionand the like. Other application methods which are generally employed bythose skilled in the art, however, can also show the desired effect ofthe present invention.

EXAMPLES

Syntheses of the 4-quinolinol derivatives represented by the generalformula (I) will be specifically illustrated by way of the followingexamples which are not intended to limit the invention.

Example 1 Synthesis of 4-hydroxy-2,3-dimethyl-6-n-pentyl-quinolineCompound No. 97)

1.63 Grams of 4-n-pentylaniline and 1.44 g of ethyl 2-methylacetoacetatewere refluxed in benzene in the presence of a Lewis acid catalyst for 3hours. The reaction mixture was washed with a saturated sodiumhydrogencarbonate solution and a saturated brine and dried overanhydrous sodium sulfate. After the solvent was evaporated, theresultant intermediate was refluxed in diphenyl ether for 30 minutes andallowed to cool to produce precipitates, which were collected byfiltration under reduced pressure to obtain 1.01 g of4-hydroxy-2,3-dimethyl-6-n-pentyl-quinoline (yield 42%). Its NMRspectral data are shown in the following Table 2.

Examples 2 to 9

The following compounds were synthesized in the same way as thatdescribed in Example 1. NMR spectral data of the thus-obtained compoundsare shown in the following Table 2.

Example 2 Compound No. 107 (yield 64%) Example 3 Compound No. 111 (yield56%) Example 4 Compound No. 125 (yield 22%) Example 5 Compound No. 131(yield 25%) Example 6 Compound No. 135 (yield 24%) Example 7 CompoundNo. 152 (yield 34%) Example 8 Compound No. 154 (yield 52%) Example 9Compound No. 156 (yield 52%)

Example 10 Synthesis of 4-acetoxy-2,3-dimethyl-6-n-pentyl-quinoline(Compound No. 98)

100 Milligrams of 4-hydroxy-2,3-dimethyl-6-n-pentyl-quinoline (CompoundNo. 97) was stirred in 2 ml of acetic anhydride at 120° C. for 4 hours.After the solvent was evaporated, 20 ml of ethyl acetate was added andthe reaction mixture was washed with an aqueous saturated sodiumhydrogencarbonate solution and a saturated brine and dried overanhydrous sodium sulfate. After the solvent was evaporated under reducedpressure, the resultant crude product was purified by columnchromatography on silica gel (WAKOGEL® C-100) eluting withn-hexane/ethyl acetate (5:1) to obtain 87.4 mg of4-acetoxy-2,3-dimethyl-6-n-pentyl-quinoline (yield 74%). Its NMRspectral data are shown in the following Table 2.

Examples 11 to 18

The following compounds were synthesized in the same way as thatdescribed in Example 10. NMR spectral data of the thus-obtainedcompounds are shown in the following Table 2.

Example 11 Compound No. 108 (yield 62%) Example 12 Compound No. 112(yield 68%) Example 13 Compound No. 126 (yield 74%) Example 14 CompoundNo. 132 (yield 8%) Example 15 Compound No. 136 (yield 76%) Example 16Compound No. 153 (yield 59%) Example 17 Compound No. 155 (yield 94%)Example 18 Compound No. 157 (yield 87%)

Example 19 Synthesis of4-acetoxy-6-(2-buten-2-yl)-2,3,8-trimethylquinoline (Compound No. 360)

26.6 Grams of 6-bromo-4-hydroxy-2,3,8-trimethylquinoline synthesized inthe same way as that described in Example 1 was suspended in 70 ml ofdimethylformamide, to which 4.4 g of 60% sodium hydride was added undercooling with ice and then the mixture was stirred at room temperaturefor 30 minutes. 19 Grams of benzyl bromide was added dropwise to thereaction mixture under cooling with ice and the mixture was allowed toreact at room temperature overnight. After 50 ml of water was added, thereaction mixture was extracted with ethyl acetate and the organic layerwas washed with a saturated brine and dried over anhydrous sodiumsulfate overnight. After the solvent was evaporated under reducedpressure, the resultant crude product was purified by columnchromatography on silica gel (WAKOGEL® C-200) eluting withn-hexane/ethyl acetate (6:1) to obtain 24.3 g of4-benzyloxy-6-bromo-2,3,8-trimethylquinoline.

4 Grams of the thus-obtained4-benzyloxy-6-bromo-2,3,8-trimethylquinoline was dissolved in 40 ml ofanhydrous tetrahydrofuran and cooled to −78° C., to which 5 ml of a 2.5M solution of n-butyllithium in n-hexane was added dropwise and themixture was stirred for 10 minutes. A solution of 1.2 g of 2-butanonedissolved in 4 ml of anhydrous tetrahydrofuran was added dropwise to thereaction mixture, which was then stirred at 0° C. for 20 minutes. After30 ml of water was added, the reaction mixture was extracted with ethylacetate and the organic layer was washed with a saturated brine anddried over anhydrous sodium sulfate overnight. After the solvent wasevaporated under reduced pressure, the residue was purified by columnchromatography on silica gel (WAKOGEL® C-200) eluting withn-hexane/ethyl acetate (7:1) to obtain 3.5 g of4-benzyloxy-6-(2-hydroxybutyl-2-yl)-2,3,8-trimethylquinoline.

To 2.8 g of the thus-obtained4-benzyloxy-6-(2-hydroxybutyl-2-yl)-2,3,8-trimethylquinoline was added10 ml of 20% sulfuric acid and the mixture was stirred at 100° C. for 80minutes. The reaction mixture was cooled to room temperature and thenneutralized with an aqueous saturated sodium carbonate solution.Precipitates were washed with water and n-hexane and then dried underreduced pressure to obtain 2.3 g of a crude product. 2.0 Grams of thecrude product was suspended in 10 ml of dimethylformamide, to which 0.37g of 60% sodium hydride was added under cooling with ice. After stirringat room temperature for 30 minutes, 0.72 g of acetyl chloride was addeddropwise under cooling with ice and the mixture was stirred at roomtemperature for 20 hours. After 15 ml of water was added, the reactionmixture was stirred and then extracted with ethyl acetate. The organiclayer was washed with a saturated brine and then dried over anhydroussodium sulfate overnight. After the solvent was evaporated under reducedpressure, the crude product was purified by column chromatography onsilica gel (WAKOGEL® C-200) eluting with n-hexane/ethyl acetate (9:1) toobtain 1.6 g of 4-acetoxy-6-(2-buten-2-yl)-2,3,8-trimethylquinoline(yield 42%). Its NMR spectral data are shown in the following Table 2.

Example 20 Synthesis of4-acetoxy-6-(2-buten-2-yl)-8-fluoro-2,3-dimethylquinoline (Compound No.362)

4-Acetoxy-6-(2-buten-2-yl)-8-fluoro-2,3-dimethylquinoline wassynthesized in the same way as that described in Example 19 using6-bromo-4-hydroxy-8-fluoro-2,3-dimethylquinoline as a starting material(yield 17%). NMR spectral data of the thus-obtained compounds are shownin the following Table 2.

Example 21 Synthesis of 4-acetoxy-6-s-butyl-2,3,8-trimethylguinoline(Compound No. 206)

To 0.41 g of 4-acetoxy-6-(2-buten-2-yl)-2,3,8-trimethylquinolineobtained in the same way as that described in Example 19 and 0.06 g of10% palladium-carbon, 6 ml of methanol was added and hydrogen was passedtherethrough to react for 16 hours at room temperature with stirring.The reaction mixture was filtered and the residue was washed twice with2 ml of methanol. The solvent was evaporated under reduced pressure toobtain 0.37 g of 4-acetoxy-6-s-butyl-2,3,8-trimethylquinoline (yield90%). Its NMR spectral data are shown in the following Table 2.

Example 22 Synthesis of4-acetoxy-6-s-butyl-8-fluoro-2,3-dimethylquinoline (Compound No. 212)

0.27 Grams of 4-acetoxy-6-s-butyl-8-fluoro-2,3-dimethylquinoline wasobtained using 0.37 g of4-acetoxy-6-(2-buten-2-yl)-8-fluoro-2,3-dimethylquinoline obtained inExample 20 as a starting material in the same way as that described inExample 21 (yield 72%). Its NMR spectral data are shown in the followingTable 2.

Example 23 Synthesis of4-acetoxy-6-c-pentyl-8-methyl-2.3-dimethylquinoline (Compound No. 352)

4-Acetoxy-6-c-pentyl-8-methyl-2,3-dimethylquinoline was obtained in thesame way as that described in Example 21 (yield 37%).

Example 24 Synthesis of4-acetoxy-6-s-butyl-8-chloro-2,3-dimethylquinoline (Compound No. 214)

4.9 Grams of 4-s-butyl-aniline was dissolved in dimethylformamide, towhich 4 g of N-chloro-succinimide dissolved in 20 ml ofdimethylformamide was added dropwise at room temperature and the mixturewas stirred overnight. The reaction mixture was poured into 100 ml ofwater, which was extracted with n-hexane. The organic layer was washedwith a saturated brine, dried over anhydrous sodium sulfate and thesolvent was evaporated under reduced pressure. Using the resultant crude4-s-butyl-2-chloroaniline in the same way as that described in Example1, 4-hydroxy-6-s-butyl-8-chloro-2,3-dimethylquinoline was obtained.Using it as a starting material, 287.5 mg of4-acetoxy-6-s-butyl-8-chloro-2,3-dimethylquinoline was obtained in thesame way as that described in Example 10 (yield 17%). Its NMR spectraldata are shown in the following Table 2.

Examples 25 and 26

The following compounds were synthesized in the same way as thatdescribed in Example 23. NMR spectral data of the thus-obtainedcompounds are shown in the following Table 2.

Example 25 Compound No. 216 (yield 31%) Example 26 Compound No. 218(yield 8%)

Example 27 Synthesis of4-acetoxy-6-s-butyl-8-methoxy-2,3-dimethylqunoline (Compound No. 220)

4-s-Butyl-2-methoxyaniline was obtained using 3-methoxyacetophenone as astarting material according to various known reactions. Using 530 mg ofthe thus-obtained 4-s-butyl-2-methoxyaniline, 264 mg of4-acetoxy-6-s-butyl-8-methoxy-2,3-dimethylquinoline was obtained in thesame way as that described in Examples 1 and 10 (yield 40%). Its NMRspectral data are shown in the following Table 2.

Examples 28 to 32

The following compounds were synthesized in the same way as thatdescribed in Example 26. NMR spectral data of the thus-obtainedcompounds are shown in the following table 2.

Example 28 Compound No. 262 (yield 53%) Example 29 Compound No. 268(yield 42%) Example 30 Compound No. 274 (yield 49%) Example 31 CompoundNo. 280 (yield 39%) Example 32 Compound No. 348 (yield 40%)

Example 33 Synthesis of4-acetoxy-6-s-butyl-8-formyl-2,3-dimethylquinoline (Compound No. 356)

5 Grams of 4-hydroxy-6-s-butyl-8-bromo-2,3-dimethylquinoline synthesizedin the same way as that described in Example 1 was suspended in 20 ml ofdimethylformamide, to which 700 mg of 60% sodium hydride was added undercooling with ice and the mixture was stirred at room temperature for 30minutes. To the reaction mixture was added dropwise 3 g of benzylbromide under cooling with ice and the mixture was allowed to react atroom temperature overnight. After the addition of 50 ml of water, thereaction mixture was extracted with ethyl acetate. The organic layer waswashed with a saturated brine and dried over anhydrous sodium sulfateovernight. After the solvent was evaporated under reduced pressure, theresultant crude product was purified by column chromatography on silicagel (WAKOGEL® C-200) eluting with n-hexane to obtain 2.5 g of4-benzyloxy-6-s-butyl-8-bromo-2,3-dimethylquinoline. 2.5 Grams of thethus-obtained 4-benzyloxy-6-s-butyl-8-bromo-2,3-dimethylquinoline wasdissolved in 25 ml of anhydrous tetrahydrofuran and cooled to −78° C.,to which 2.8 ml of a 2.5 M solution of n-butyl lithium in n-hexane wasadded dropwise and the mixture was stirred for 10 minutes. One ml ofmethyl formate dissolved in 2 ml of anhydrous tetrahydrofuran was addeddropwise to the reaction mixture and the mixture was stirred at 0° C.for 30 minutes. After the addition of 50 ml of water, the reactionmixture was extracted with ethyl acetate. The organic layer was washedwith an aqueous saturated ammonium chloride solution and a saturatedbrine and then dried over anhydrous sodium sulfate. After the solventwas evaporated under reduced pressure, the residue was purified bycolumn chromatography on silica gel (WAKOGEL® C-200) eluting withn-hexane/ethyl acetate (20:1) to obtain 800 mg of4-benzyloxy-6-s-butyl-8-formyl-2,3-dimethylquinoline.

800 Milligrams of the resultant4-benzyloxy-6-s-butyl-8-formyl-2,3-dimethylquinoline was dissolved in2.5 ml of 20% sulfuric acid and stirred at 100° C. for 1 hour. Aftercooling to room temperature, the reaction mixture was neutralized withan aqueous saturated sodium hydrogencarbonate solution to produceprecipitates, which were washed with water and n-hexane and then driedunder reduced pressure to obtain 490 mg of4-hydroxy-6-s-butyl-8-formyl-2,3-dimethylquinoline. 440 Milligrams of4-hydroxy-6-s-butyl-8-formyl-2,3-dimethylquinoline was suspended in amixture of 3 ml of acetic anhydride and 0.5 ml of pyridine and themixture was stirred at 120° C. for 1.5 hours. The reaction mixture wascooled to room temperature, neutralized with an aqueous saturated sodiumhydrogencarbonate solution and extracted with ethyl acetate. Theresultant organic layer was washed with a saturated brine and dried overanhydrous sodium sulfate. After the solvent was evaporated, theresultant crude product was purified by column chromatography on silicagel (WAKOGEL® C-200) eluting with n-hexane/ethyl acetate (10:1) toobtain 220 mg of 4-acetoxy-6-s-butyl-8-formyl-2,3-dimethylquinoline(yield 13%). Its NMR spectral data are shown in the following Table 2.

Example 34 Synthesis of4-acetoxy-6-s-butyl-8-hydroxymethyl-2,3-dimethylquinoline (Compound No.340)

210 Milligrams of 4-acetoxy-6-s-butyl-8-formyl-2,3-dimethylquinolineobtained in Example 33 was dissolved in 4 ml of methanol, to which 7 mgof sodium borohydride dissolved in 4 ml of methanol was added dropwiseand the mixture was stirred at room temperature for 1 minute. After theaddition of 20 ml of water, the reaction mixture was extracted withethyl acetate. The resultant organic layer was washed with a saturatedbrine and dried over anhydrous sodium sulfate. After the solvent wasevaporated under reduced pressure, the resultant crude product waspurified by column chromatography on silica gel (WAKOGEL® C-200) elutingwith n-hexane/ethyl acetate (10:1) to obtain 186 mg of4-acetoxy-6-s-butyl-8-hydroxymethyl-2,3-dimethylquinoline (yield 84%).Its NMR spectral data are shown in the following Table 2.

Example 35 Synthesis of4-acetoxy-6-s-butyl-8-chloromethyl-2,3-dimethylquinoline (Compound No.344)

50 Milligrams of4-acetoxy-6-s-butyl-8-hydroxymethyl-2,3-dimethylquinoline obtained inExample 34 was dissolved in 0.3 ml of thionyl chloride and stirred atroom temperature for 4.5 hours. After thionyl chloride was evaporatedunder reduced pressure, 0.5 ml of acetic anhydride was added to theresultant crude product and the mixture was stirred at 120° C. for 2hours. After acetic anhydride was evaporated under reduced pressure, theresultant residue was purified by column chromatography on silica gel(WAKOGEL® C-200) eluting with n-hexane/ethyl acetate (20:1) to obtain12.5 mg of 4-acetoxy-6-s-butyl-8-chloromethyl-2,3-dimethylquinoline(yield 23.5%). Its NMR spectral data are shown in the following Table 2.

TABLE 2 com- pound No. NMR spectral data  97 11.37(1H, s), 7.83(1H, s),7.42(1H, dd, J₁ = 8.6, J₂ = 1.6), 7.39(1H, d, J = 8.6), 2.65(2H, t, J =7.4), 2.36(3H, s), 1.96(3H, s), 1.59(2H, m), 1.29(4H, m), 0.85(3H, t, J= 6.8) solvent: DMSO-d₆  98 7.94(1H, d, J = 8.7), 7.49(1H, dd, J₁ = 8.7,J₂ = 1.7), 7.42(1H, s), 2.75(2H, m), 2.71(3H, s), 2.52(3H, s), 2.25(3H,s), 1.68(2H, m), 1.34(4H, m), 0.90(3H, t, J = 6.7) solvent: CDCl₃ 10711.36(1H, s), 7.83(1H, br.s), 7.39(2H, m), 2.65(2H, m), 2.35(3H, s),1.95(3H, s), 1.58(2H, m), 1.27(6H, m), 0.85(3H, t, J = 6.9) solvent:DMSO-d₆ 108 7.92(1H, d, J = 8.6), 7.49(1H, d, J = 8.6), 7.42(1H, s),2.75(2H, t, J = 7.8), 2.71(3H, s), 2.52(3H, s), 2.24(3H, s), 1.67(2H,m), 1.39˜1.28(6H, m), 0.88(3H, t, J = 7.6) solvent: CDCl₃ 111 11.32(1H,s), 7.85(1H, d, J = 2.0), 7.44(1H, dd, J₁ = 8.5, J₂ = 2.2), 7.38(1H, d,J = 8.6), 2.60(1H, m), 2.34(3H, s), 1.95(3H, s), 1.81(4H, m), 1.70(1H,m), 1.39(4H, m), 1.25(1H, m) solvent: DMSO-d₆ 112 8.18(1H, d, J = 2.0),7.93(1H, d, J = 8.8), 7.53(1H, dd, J₁ = 8.8, J₂ = 2.0), 2.86(3H, s),2.72(1H, m), 2.70(3H, s), 2.52(3H, s), 1.80(4H, m), 1.77(1H, m),1.46(4H, m), 1.31(1H, m) solvent: CDCl₃ 125 11.35(1H, s), 7.83(1H,br.s), 7.40(2H, m), 2.65(2H, m), 2.35(3H, s), 1.95(3H, s), 1.58(2H, m),1.27˜1.23(10H, m), 0.84(3H, t, J = 6.6) solvent: DMSO-d₆ 126 7.93(1H, d,J = 8.8), 7.49(1H, dd, J₁ = 8.8, J₂ = 1.9), 7.42(1H, d, J = 1.2),2.75(2H, t, J = 7.8), 2.71(3H, s), 2.52(3H, s), 2.24(3H, s),1.71˜1.25(10H, m), 0.87(3H, t, J = 6.9) solvent: CDCl₃ 131 11.78(1H, s),8.33(1H, br.s), 7.86(1H, dd, J₁ = 8.8, J₂ = 2.0), 7.66(1H, d, J = 8.8),2.40(3H, s), 1.98(3H, s) solvent: DMSO-d₆ 132 8.12(1H, d, J = 9.0),8.00(1H, br.s), 7.82(1H, dd, J₁ = 9.0, J₂ = 2.0), 2.54(3H, s), 2.30(3H,s), 2.28(3H, s) solvent: CDCl₃ 135 11.53(1H, s), 7.54(1H, d, J = 9.0),7.47(1H, d, J = 3.1), 7.41(2H, dd, J₁ = 8.6, J₂ = 7.5), 7.37(2H, dd, J₁= 9.0, J₂ = 3.1), 7.16(1H, t, J = 7.5), 7.04(2H, dd, J₂ = 8.6, J₂ =1.0), 2.37(3H, s), 1.94(3H, s) solvent: DMSO-d₆ 136 7.98(1H, d, J =9.4), 7.38(2H, br.d, J = 8.6), 7.35(1H, d, J = 2.7), 7.18(1H, d, J =2.7), 7.14(1H, br.d, J = 6.7), 7.06(2H, br.dd, J₁ = 8.6, J₂ = 0.8),2.71(3H, s), 2.40(3H, s) solvent: CDCl₃ 152 11.83(1H, s), 7.90(1H, s),7.43(2H, s), 2.97(1H, t), 2.68(3H, m), 2.04(2H, t), 1.60(2H, t),1.23(3H, d), 0.77(3H, t) solvent: DMSO-d₆ 153 7.97(1H, d, J = 8.8),7.54(1H, d, J = 1.9), 7.51(1H, dd, J₁ = 8.8, J₂ = 1.9), 3.19(2H, t, J =7.7), 2.95(2H, t, J = 7.4), 2.76(1H, m), 2.49(3H, s), 2.20(2H, quint, J= 7.4), 1.67(2H, quint, J = 7.4), 1.31(3H, d, J = 6.9), 0.84(3H, t, J =7.3) solvent: CDCl₃ 154 11.20(1H, s), 7.36(1H, d, J = 8.7), 7.21(1H, d,J = 2.0), 7.10(1H, dd, J₁ = 8.7, J₂ = 2.0), 3.38(4H, q, J = 6.9),2.34(3H, s), 1.97(3H, s), 1.11(6H, t, J = 6.9) solvent: DMSO-d₆ 1558.56(1H, d, J = 2.8), 7.85(1H, d, J = 9.3), 7.20(1H, dd, J₁ = 9.3, J₂ =2.8), 3.44(4H, q, J = 7.0), 2.64(3H, s), 2.48(3H, s), 2.21(3H, s),1.21(6H, t, J = 7.0) solvent: CDCl₃ 156 11.23(1H, s), 7.40(3H, s),3.86(4H, m), 3.11(4H, m), 2.35(3H, s), 2.06(3H, s) solvent: DMSO-d₆ 1578.85(1H, d, J = 2.7), 7.90(1H, d, J = 9.2), 7.39(1H, dd, J₁ = 9.2, J₂ =2.7), 3.90(4H, m), 3.26(4H, m), 2.67(3H, s), 2.50(3H, s), 2.23(3H, s)solvent: CDCl₃ 206 7.31(1H, s), 7.24(1H, s), 2.74(3H, s), 2.69(3H, s),2.67(1H, m) 2.48(3H, s), 2.21(3H, s), 1.63(2H, m), 1.27(3H, d, J = 7.0)0.81(3H, t, J = 7.0) solvent: CDCl₃ 212 7.21(1H, m), 7.19(1H, m),2.74(1H, m), 2.73(3H, s), 2.50(3H, s) 2.24(3H, s), 1.62(2H, m), 1.27(3H,d, J = 7.0), 0.82(3H, t, J = 7.0) solvent: CDCl₃ 214 7.63(1H, d, J =2.0), 7.34(1H, d, J = 2.0), 2.77(3H, s), 2.73(1H, m), 2.51(3H, s),2.25(3H, s), 1.65(2H, m), 1.30(3H, d, J = 6.9), 0.84(3H, t, J = 7.3)solvent: CDCl₃ 216 7.62(1H, d, J = 1.9), 7.35(1H, d, J = 1.7), 2.77(3H,s), 2.73(2H, t, J = 7.8) 2.51(3H, s), 2.25(3H, s), 1.66(2H, m), 1.39(2H,m), 0.95(3H, t, J = 7.3) solvent: CDCl₃ 218 7.83(1H, d, J = 2.0),7.51(1H, d, J = 1.9), 2.77(3H, s), 2.51(3H, s) 2.25(3H, s), 1.39(9H, s)solvent: CDCl₃ 220 7.01(1H, d, J = 1.5), 6.84(1H, d, J = 1.5), 4.06(3H,s), 2.75(3H, s) 2.71(1H, m), 2.50(3H, s), 2.24(3H, s), 1.66(2H, m),1.30(3H, d, J = 6.8), 0.85(3H, t, J = 7.5) solvent: CDCl₃ 262 7.31(1H,s), 7.27(1H, s), 2.74(3H, s), 2.70(3H, s), 2.50(3H, s), 2.46(3H, s),2.23(3H, s) solvent: CDCl₃ 268 7.34(1H, s), 7.28(1H, s), 3.25(2H, q, J =7.5), 2.77(2H, q, J = 7.5) 2.70(3H, s), 2.23(3H, s), 1.35(3H, t, J =7.5), 1.30(3H, t, J = 7.6) solvent: CDCl₃ 274 7.40(1H, d, J = 2.0),7.28(1H, d, J = 1.9), 4.31(1H, m), 3.04(1H, m) 2.69(3H, s), 2.50(3H, s),2.23(3H, s), 1.36(6H, d, J = 6.8), 1.31(6H, d, J = 7.0) solvent: CDCl₃280 7.30(1H, d, J = 1.7), 7.24(1H, d, J = 1.7), 4.13(1H, m), 2.73(1H,m), 2.69(3H, s), 2.51(3H, s), 2.22(3H, s), 1.61˜1.84(4H, m) 1.31(3H, d,J = 7.0), 1.30(3H, d, J = 7.3), 0.87(3H, t, J = 7.3), 0.83(3H, t, J =7.0) solvent: CDCl₃ 334 7.90(1H, d J = 8.5), 7.44(1H, dd J1 = 8.5, J2 =2.0), 7.37(1H, d J = 2.0), 2.71(3H, s), 2.65(2H, s), 2.51(3H, s),2.56(3H, s), 0.93(9H, s) solvent: CDCl₃ 338 7.58(1H, d J = 1.7),7.31(1H, d J = 1.7), 2.78(3H, s), 2.63(2H, s), 2.51(3H, s), 2.27(3H, s),0.95(9H, s) solvent: CDCl₃ 340 7.34(1H, d, J = 1.7), 7.33(1H, d, J =1.7), 5.64(1H, br.s), 5.12(2H, s) 2.75(1H, m), 2.70(3H, m), 2.51(3H, s),2.25(3H, s), 1.65(2H, m) 1.29(3H, d, J = 6.8), 0.83(3H, t, J = 7.3)solvent: CDCl₃ 344 7.64(1H, d, J = 2.0), 7.39(1H, d, J = 1.9), 5.32(2H,s), 2.75(1H, m), 2.71(3H, s), 2.51(3H, s), 2.24(3H, s), 1.66(2H, m),1.31(3H, d =, J = 6.8), 0.84(3H, t, J = 7.3) solvent: CDCl₃ 348 7.33(1H,d, J = 2.0), 7.25(1H, d, J = 2.0), 3.25(2H, q, J = 7.4), 2.73(1H, m),2.70(3H, s), 2.50(3H, s), 2.23(3H, s), 1.65(2H, m), 1.36(3H, t, J =7.6), 1.29(3H, d, J = 7.0), 0.84(3H, t, J = 7.4) solvent: CDCl₃ 3527.37(1H, s), 7.29(1H, s), 3.08(1H, m), 2.73(3H,s), 2.69(3H, s), 2.48(3H,s), 2.09(3H, s), 1.7˜2.2(8H, m) solvent: CDCl₃ 356 11.43(1H, s),8.12(1H, d, J = 2.2), 7.69(1H, d, J = 2.0), 2.82(1H, m), 2.76(3H, s),2.54(3H, s), 2.28(3H, s), 1.69(2H, m), 1.32(3H, d, J = 6.8), 0.83(3H, t,J = 7.3) solvent: CDCl₃ 360 7.53(1H, s), 7.40(1H, s), 5.95(1H, m),2.74(3H, s), 2.69(3H, s), 2.50(3H, s), 2.22(3H, s), 2.07(3H, s),1.82(3H, d, J = 6.8) solvent: CDCl₃ 362 7.39-7.47(2H, m), 5.98(1H, m),2.73(3H, s), 2.49(3H, s), 2.24 (3H, s), 2.06(3H, s), 1.83(3H, d, J =7.1) solvent: CDCl₃

In the above tables, S, d, t, q, quint and m mean singlet, doublet,triplet, quartet, quintet and multiplet, respectively.

And, DCDl₃ and DMSO-d₆ mean deuterium chloroform and deuterium DMSO,respectively.

The following ingredients: Formulation Example 1 (wettable powder) thepresent compound (Compound No. 29) 25% by weight clay 30% by weightdiatomaceous earth 35% by weight calcium lignin sulfonate 3% by weightpolyoxyethylene alkyl aryl ether 7% by weight were uniformly mixed andpulverized to obtain a wettable powder. Formulation Example 2 (dustformulation) the present compound (Compound No. 29) 2% by weight clay60% by weight talc 37% by weight calcium stearate 1% by weight wereuniformly mixed to obtain a dust formulation. Formulation Example 3(emulsifiable concentrate) the present compound (Compound No. 29) 20% byweight N,N-dimethylformamide 20% by weight xylene 50% by weightpolyoxyethylene alkyl aryl ether 10% by weight were added, uniformlymixed and dissolved to obtain an emulsifiable concentrate. FormulationExample 4 (granule) the present compound (Compound No. 29) 5% by weightbentonite 40% by weight talc 53% by weight calcium lignin sulfonate 2%by weight were uniformly mixed with grinding, to which water was added,well kneaded, granulated and then dried to obtain a granule.

Test Example 1 Test for Control Effect Against Rice Blast

A spray liquid comprising a test compound whose concentration wasadjusted to be 100 ppm by dilution with water was sprayed to a riceseedling (variety: Jikkoku) of 4-leaf stage grown in a vinyl pot of 5 cmin diameter by means of a spray gun. The air-dried rice seedling wasinoculated with a conidium suspension of Pyricularia oryzae on the dayof said application. For 40 hours after the inoculation, the riceseeding was under moist condition to complete infection with Pyriculariaoryzae and then grown in an air-conditioned greenhouse. 6 Days after theinoculation, the lesion number on the fourth-leaf was counted. Theprotective value was calculated by comparing the lesion number in atreated area with that in an untreated area. Then, control effect wasranked according to the following criterion.

A; protective value ≧80%

B; protective value 50 to 79%

C; protective value <50%

Results are shown in Table 3.

TABLE 3 com- pound No. rank 2 B 9 A 10 A 13 A 14 A 23 B 24 B 28 A 29 A31 A 44 A 45 A 46 A 47 A 48 A 49 A 54 A 55 A 56 A 57 A 61 A 62 A 63 A 65A 66 A 67 A 68 A 69 A 70 A 72 B 83 A 84 A 92 B 93 A 97 B 98 A 107 A 108A 111 B 112 A 125 B 126 A 131 B 136 A 153 B 170 A 171 B 172 A 173 A 179A 180 A 182 B 183 B 185 B 186 B 190 B 191 A 192 A 193 A 195 A 197 A 198B 199 A 200 A 206 A 212 A 214 A 216 A 218 A 220 A 262 B 268 A 274 A 340A 344 A 348 A 352 A 356 A 360 A 362 A

Test Example 2 Test for Control Effect Against Powdery Mildew ofCucurbitaceae

A spray liquid comprising a test compound whose concentration wasadjusted to be 200 ppm by dilution with water was sprayed to a cucumbergrown in a vinyl pot of 3 cm in diameter when its first foliage leaf wasdeveloped. The air-dried cucumber seedling was inoculated with aconidium suspension of Sphaerotheca fuliginea. Thereafter, the cucumberseedling was transferred in an air-conditioned greenhouse. 10 Days afterthe inoculation, the disease severity was observed. The protective valuewas calculated by comparing the disease severity in a treated area withthat in an untreated area. Then, control effect was ranked according tothe following criterion.

A; protective value ≧80%

B; protective value 50 to 79%

C; protective value <50%

Results are shown in Table 4.

TABLE 4 compound No. rank 24 A 29 B 45 B 55 A 56 A 61 B 65 A 66 A 67 A68 A 71 A 72 A 93 A 112 A 136 A 153 A 175 A 176 A 185 A 195 A 196 A 197A 214 A 216 B 218 A 268 B 340 A 344 A 348 A 356 A

Test Example 3 Test for Antifungal Activity

A test compound dissolved in acetone was mixed in a potato dextrose agarmedium (manufactured by Nissui Seiyaku K. K.) so that the finalconcentration of the test compound was 100 ppm and then poured in aPetri dish. To this Perti dish after the agar was completely solidified,a cylindrical section prepared by punching a mycelial colony of each ofplant pathogenic fungi cultured in another Petri dish by means of a corkborer was inoculated and cultured at 28 or 22° C. 48 Hours after theinoculation, the diameter of the mycelial colony was determined. Controlpercentages were calculated by comparing the diameter of the mycelialcolony in a treated area with that in an untreated area. And, antifungaleffect was ranked according to the following criterion.

A; control percentage ≧80%

B; control percentage 50 to 79%

C; control percentage <50%

Results are shown in Table 5.

TABLE 5 Compoud No. Plant pathogen 10 28 29 31 Pyricularia oryzae A B AA Rhizoctonia solani C C C C Cochlioborus miyabeanus B C B A Gibberellafujikuroi C C B A Botrytis cinerea C C B A Fusarium oxysporum f. sp.lycopersici C C B A Glomerella cingalata B B A A Sclerotinia minor C C CB Colletotrichum atramentarium B B B A Alternaria alternata Japanese C CC A pear pathotype Verticillium aibo-atrum C A A A

EFFECT OF THE INVENTION

The new 4-quinolinol derivatives represented by the general formula (I)of the present invention have an effective action as an agricultural andhorticultural fungicide.

What is claimed is:
 1. A method comprising applying a fungicide to aplant in need thereof, wherein the fungicide comprises a 4-quinolinolcompound represented by the formula (I):

or an agriculturally and horticulturally acceptable acid addition saltthereof, wherein R¹ represents a hydrogen atom, an alkali metal, analkaline earth metal, or COR⁴ in which R⁴ is a hydrogen atom, anoptionally substituted C₁-C₁₈ alkyl group, an optionally substitutedC₂-C₁₈ alkenyl group, an optionally substituted C₃-C₁₀ cycloalkyl group,an optionally substituted phenyl C₁-C₄ alkyl group, an optionallysubstituted phenoxy C₁-C₄ alkyl group, an optionally substituted arylgroup, OR⁵ in which R⁵ is an optionally substituted C₁-C₄ alkyl group,an optionally substituted aryl group, an optionally substitutedheterocycle, an optionally substituted phenyl C₁-C₄ alkyl group or anoptionally substituted phenoxy C₁-C₄ alkyl group, or NR⁶R⁷ in which R⁶and R⁷ are each a hydrogen atom, an optionally substituted C₁-C₆ alkylgroup or an optionally substituted phenyl group, or R⁶ and R⁷ togetherwith N may form a four- to six-membered ring containing one or twoheteroatoms; R² represents an optionally substituted lower alkyl group;R³ represents an optionally substituted C₁-C₁₈ alkyl group, anoptionally substituted lower alkenyl group, or an optionally substitutedlower alkoxy group; or R² and R³ together represent —(CH₂)m— in which mis 3 or 4; and W represents 1 to 4 substituents on the nucleus which maybe identical or different and each of which is a halogen atom, anoptionally substituted C₁-C₁₀ alkyl group, an optionally substitutedC₂-C₄ alkenyl group, an optionally substituted C₂-C₄ alkynyl group, anoptionally substituted C₁-C₁₀ alkoxy group, an optionally substitutedC₃-C₁₀ cycloalkyl group, an optionally substituted aryl group, anoptionally substituted aryloxy group, NR⁸R⁹ in which R⁸ and R⁹ are eacha hydrogen atom, an optionally substituted C₁-C₆ alkyl group or anoptionally substituted phenyl group, or R⁸ and R⁹ together with N mayform a four- to six-membered ring containing one or two heteroatoms,COR¹⁰ in which R¹⁰ is a hydrogen atom, an optionally substituted C₁-C₄alkyl group or an optionally substituted C₂-C₄ alkenyl group, COOR¹¹ inwhich R¹¹ is a hydrogen atom, an optionally substituted C₁-C₄ alkylgroup or an optionally substituted C₂-C₄ alkenyl group, a nitro group,or a cyano group; wherein when optional substituents present, theoptional group is selected from the group consisting of halogen, C₁-C₄alkyl group, C₁-C₄ alkoxy group, hydroxyl, nitro, formyl, and cyano. 2.The method of claim 1 wherein R¹ represents COR⁴ in which R⁴ is a C₁-C₁₈alkyl group; R² represents a C₁-C₄ alkyl group; R³ represents a C₁-C₁₈alkyl group; and W represents 1 to 4 substituents on the nucleus whichmay be identical or different and each of which is a halogen atom, anoptionally substituted C₁-C₁₀ alkyl group, an optionally substitutedC₁-C₁₀ cycloalkyl group.
 3. The method of claim 2, wherein R¹ is CH₃CO;R² and R³ are each CH³; and W represents two substituents which are6-alkyl group or 6 C₃-C₁₀ cycloalkyl group optionally substituted byC₁-C₄ alkyl group and 8-halogen.
 4. The method of claim 3, wherein W are6-s-C₄H₉ and 8-F.
 5. The method of claim 3, wherein W are 6-t-C₄H₉ and8-Cl.
 6. The method of claim 3, wherein W are 6-t-C₄H₉ and 8-F.
 7. Themethod of claim 3, wherein W are 6-(1-methyl-cyclohexyl) and 8-F.